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Regenerative Polysulfide-Scavenging Layers Enabling LithiumSulfur Batteries with High Energy Density and Prolonged Cycling Life Fang Liu, Qiangfeng Xiao, Hao Bin Wu, Fei sun, Xiaoyan Liu, Fan Li, Zaiyuan Le, LI SHEN, Ge Wang, Mei Cai, and Yunfeng Lu ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.6b07603 • Publication Date (Web): 11 Feb 2017 Downloaded from http://pubs.acs.org on February 12, 2017

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Regenerative Polysulfide-Scavenging Layers Enabling Lithium-Sulfur Batteries with High Energy Density and Prolonged Cycling Life Fang Liu1, Qiangfeng Xiao2, Hao Bin Wu1, Fei Sun1, Xiaoyan Liu1, Fan Li1, Zaiyuan Le1, Li Shen1, Ge Wang3, Mei Cai2 and Yunfeng Lu1,*

1

Department of Chemical and Biomolecular Engineering, University of California, Los Angeles,

CA 90095, USA. 2

General Motors Research and Development Center, 30500 Mount Road, Warren, MI 48090,

USA. 3

Department of Materials Science and Engineering, University of Science and Technology

Beijing, Beijing, 100083, China.

*Email: [email protected]

1 ACS Paragon Plus Environment

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ABSTRACT: Lithium-sulfur batteries, notable for high theoretical energy density, environmental benignity and low cost, hold great potentials for next-generation energy storage. Polysulfides, the intermediates generated during cycling, may shuttle between electrodes, compromising the energy density and cycling life. We report herein a class of regenerative polysulfide-scavenging layers (RSL), which effectively immobilize and regenerate polysulfides, especially for electrodes with high sulfur loadings (e.g., 6 mg cm-2). The resulted cells exhibit high gravimetric energy density of 365 Wh kg-1, initial areal capacity of 7.94 mAh cm-2, low self-discharge rate of 2.45% after resting for 3 days and dramatically prolonged cycling life. Such blocking effects have been thoroughly investigated and correlated with the work functions of the oxides, as well as their bond energies with polysulfides. This work offers not only a class of RSL to mitigate shuttling effect, but also a quantified design framework for advanced lithium-sulfur batteries.

KEYWORDS: lithium-sulfur battery, metal oxides, polysulfide-scavenging, polysulfideregeneration, physisorption, chemisorption.


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Lithium-sulfur (Li-S) batteries, notable for high theoretical energy capacity, environmental benignity and low cost, hold great potentials for next-generation energy storage.1,2 Broad adaption of Li-S batteries, however, has been hampered by their low gravimetric energy density and short cycling life. The limitations are mainly resulted from the low electronic/ionic conductivity, large volumetric change of sulfur species and shuttling effect. During cycling, lithium polysulfides (Li2Sn, n = 4-8) may diffuse throughout the cells, triggering parasitic reactions with lithium-metal anodes and consequently compromising the cycling life of the cells.3 Extensive efforts have been made to address such limitations. One focus is to infiltrate sulfur into conductive scaffolds.4-10 Polysulfides, which are generated continuously during the discharging process, may still diffuse throughout the cells. To restrain the diffusion, various materials have been coated onto the separators. For example, polymer layers,11–13 represented by Nafion with sulfonated moieties (-SO3-), may block the diffusion of polysulfides anions through electrostatic repulsion. High loading of high-cost Nafion, however, is required to achieve sufficient blocking effect (e.g., 0.7 mg cm-2 loading of Nafion for cathodes with 0.53 mg cm-2 loading of sulfur).12 The metal-oxide layers, represented by V2O5 layers, allow effective transport of Li+ ions while block the diffusion of polysulfides.14 Such inorganic coatings, however, are generally achieved by sol-gel process, which are often brittle and defective. In addition, extensive research on carbon-coated separators has been conducted, utilizing CNTs,15-20 graphene,21,22 carbon black,23–25 carbon fibers,26 porous carbons,27–30 as well as composites of carbons and non-reactive inorganic moieties (e.g., Al2O3,31 TiO232 and SiO233)as adsorbents. Through physisorption of polysulfides, such carbon-coated separators help mitigate the shuttling effect; however, the effectiveness and enhancement is mostly limited to cathodes with low sulfur


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loadings (< 2 mg cm-2). Therefore, it remains challenging to develop effective polysulfideblocking layers for high loading cathodes (> 6 mg cm-2) to achieve high specific energy (> 350 Wh kg-1) and prolonged cycling life (>100 cycles).34 We report herein an effective polysulfide-blocking strategy based on regenerative polysulfide-scavenging layers (RSL), which can dynamically block the diffusion of polysulfides and regenerate themselves during cycling. As illustrated in Figure 1, the RSL are made from flexible and conductive membranes of carbon nanotubes (CNTs), in which the center layers are embedded with nanowires or nanocrystals of metal oxides. The outward diffused polysulfides are adsorbed by or reacted with the RSL, forming [Polysulfides-RSL] complexes and being immobilized within the RSL. Subsequent charging process stripes away these polysulfides and regenerates the RSL. This combination of large amount of polysulfides scavenged and the regenerative capability affords highly effective and dynamic scavenging of polysulfides, leading to dramatically reduced lithium corrosion and prolonged cycling life, especially for electrodes with high sulfur loadings. Furthermore, the RSL are electronically conductive and mechanically robust, thus further enhance the performance of the cells. The scavenging effects, which are originated from the physisorption and chemical reaction with polysulfides, have been thoroughly investigated and correlated with electrochemical performance of the cells.


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Figure 1. Schematic presentation of a Li-S cell with a regenerative polysulfide-scavenging layers (RSL). The RSL is made from a CNTs membrane of which the center is embedded with interpenetrating nanowires or nanocrystals of metal oxides. (i) During discharging, as-generated polysulfides are adsorbed by or reacted with the RSL, immobilized onto the RSL denoted as [Polysulfides-RSL] complexes. (ii) Subsequent charging process strips away the immobilized species and regenerates the RSL, enabling dynamic blocking of the polysulfides.

RESULTS AND DISCUSSION Synthesis and characterization of the RSL. To demonstrate this concept, V2O5 nanowires were selected as a model oxide, which has been extensively explored for electrochemical energy storage with high capacity (294 mAh g-1 with 2 Li+ insertion/extraction per unit), fast Li+ intercalation kinetics, and long cycling life (> 500 cycles).35 Besides, it exhibits a redox window from 1.8 to 4.0 V (vs. Li+/Li), matching well with the redox window of sulfur (1.7 to 2.8 V vs. Li+/Li). We have recently synthesized the composites of V2O5 nanowires intertwined with CNTs using hydrothermal reaction.36,37 Based on such composites, CNTs/V2O5 RSL were fabricated by sequentially filtration of the dispersion of CNTs, CNTs/V2O5 composite, and CNTs onto


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commercial polypropylene separators. During this fabrication process, CNTs from the dispersions can be entangled forming CNTs networks for effective electron conduction, allowing effective redox reactions within the CNTs/V2O5 RSL. In this context, sufficient conductivity is essential to endow the RSL with scavenging capability for polysulfides and regenerative ability (Supplementary Figure 1). Figures 2a and 2b present the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of the CNTs/V2O5 composites, respectively, demonstrating a continuously fibrous structure made from interpenetrative V2O5 nanowires and CNTs. The nanowires are porous (see inset) with diameters of ~30 nm. Figure 2c exhibits a high-resolution TEM (HRTEM) image and selected area Fast Fourier Transformation (FFT) of the V2O5 nanowires, confirming its layered crystalline structure. The HRTEM image displays a d-spacing of 0.211 nm, which is consistent with the (020) lattice plane of V2O5. X-ray diffraction (XRD) analysis (Figure 2d) reveals the characteristic peaks at 9.2, 13.2, 26.4, 29.1 and 41.8◦, corresponding to the (001), (002), (111), (200) and (020) planes of V2O5 with a layered structure, respectively.38,39 Measured by thermogravimetric analysis (TGA), the weight percent of CNTs in the composites is ~9.8 % (Supplementary Figure 2). Figure 2e shows a cross-sectional image of RSL with ~15 µm in thickness, which contains porous CNTs layers sandwiched with a V2O5-rich layer in the center. Such RSL are also flexible with good mechanical strength (see the digital photographs presented in Supplementary Figure 3).


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Figure 2. Structure of the CNTs/V2O5 composites and CNTs/V2O5 RSL. a. SEM image of a CNTs/V2O5 composite with a fibrous structure made from interpenetrative V2O5 nanowires and CNTs. b. TEM images of the CNTs/V2O5 composites, showing a continuous and porous structure with average nanowire diameter of ~30 nm. c. High-resolution TEM image and its corresponding selected area FFT image (inset) of the CNTs/V2O5 composites. d. X-ray diffraction profile of the CNTs/V2O5 composites. e. Cross-section SEM image of a CNTs/V2O5 RSL made from two CNTs layers and a sandwiched CNTs/V2O5 layer. Scale bars are a. 500 nm; b. 50 nm, 10 nm (inset); c. 5 nm, 1 nm (inset); e. 5 µm.

Electrochemical studies. The redox behavior of the sulfur cathodes with Celgard polypropylene (PP) separator or the CNTs/V2O5 RSL was examined with cyclic voltammetry (CV) at a scanning rate of 0.2 mV s-1 (Figure 3a). To deconvolute the attribution of the CNTs and the V2O5 moieties, CNTs RSL were fabricated with CNTs via a similar method (see Supplementary Table 1) and integrated with sulfur cathode. All three cathodes present two cathodic peaks corresponding to the reduction of element sulfur and high-order lithium polysulfides, and an anodic peak corresponding to the oxidation of sulfur species.32 The electrode without RSL shows sluggish electrochemical kinetic, which is resulted from the low electronic and ionic conductivity of the sulfur species.4,15,40 By incorporating the CNTs/V2O5 RSL or the CNTs RSL, the cathode exhibits well-defined redox peaks with less polarization.


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Figure 3b further compares the electrochemical impedance spectroscopy (EIS) of the electrodes, indicating a charge transfer resistance of 160, 70 or 55 ohms with Celgard PP separator, CNTs/V2O5 RSL or CNTs RSL, respectively. The improved conductivity enhances the rate performance and capacity of the electrode. As shown in Figure 3c, the sulfur electrode with Celgard PP separator exhibits an initial capacity of 663 mAh g-1 at 0.3 C rate (1 C = 1675 mA g1

) and reversible capacities of 521, 396, 352, and 272 mAh g-1 at 0.5, 1, 2 and 4 C rates,

respectively. In addition, the sulfur electrode with CNTs RSL presents an initial capacity of 1396 mAh g-1 at 0.3 C rate and reversible capacities of 901, 768, 694 and 614 mAh g-1 at 0.5, 1, 2 and 4 C rates, respectively. In contrast, the sulfur electrode with the CNTs/V2O5 RSL delivers a much higher initial capacity of 1513 mAh g-1 at 0.3 C rate and reversible capacities of 1170, 1063, 954 and 858 mAh g-1 at 0.5, 1, 2 and 4 C rates, respectively. As-presented electrochemical performance clearly suggests that the incorporation of CNTs/V2O5 RSL leads to significantly improved rate performance and the utilization of sulfur. Furthermore, Figure 3d compares the cycling stability of Li-S cells with Celgard PP separator or RSL at 1 C rate. With the conventional separator, a low initial capacity of 315 mAh g-1 is observed, which decreases to 124 mAh g-1 after 250 cycles, while the cell with the CNTs/V2O5 RSL delivers a much higher initial capacity of 1068 mAh g-1 and a reversible capacity of 939 mAh g-1 after 250 cycles. As shown in Figure 3d, the cell with the CNTs RSL exhibits a reversible capacity of 498 mAh g-1 after 250 cycles, which is significantly lower than that with the CNTs/V2O5 RSL. Furthermore, the one with the CNTs/V2O5 RSL retains near 100% efficiency after 200 cycles, while the one with the CNTs RSL suffers from severe shuttling effect with dramatically reduced Coulombic efficiency. This comparison indicates that the enhancement in cycling stability is mainly contributed by the V2O5 moieties. For further


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comparison, thicker CNTs RSL (denoted as CNTs(2) RSL) were also fabricated, which contain ~2.5 folds of the CNTs. It was found that the cell with CNTs(2) RSL only maintains a reversible capacity of 730 mAh g-1 after 250 cycles (Supplementary Figure 4). Consistently, a series of CNTs/V2O5 RSL with fixed total mass but different mass ratios between V2O5 and CNTs were also fabricated. With CNTs layers facilitating charge transfer and regeneration of polysulfides, CNTs/V2O5 RSL with higher percentage of V2O5 enables better cycling stability of lithiumsulfur batteries. (Supplementary Figure 5).

Figure 3. Electrochemical performance of Li-S cells with Celgard PP separator, CNTs RSL or CNTs/V2O5 RSL. a. Cyclic voltammetries obtained at a scanning rate of 0.2 mV s-1. b. Nyquist plots showing a reduced charge-transfer resistance with the RSL. c. Rate performance at 0.3 C, 0.5 C, 1 C, 2 C, 4 C and 0.3 C rate (sulfur loading 2 mg cm-2). d. e. & f. Galvanostatic cycling performance at 1 C rate, 0.1 C rate and 0.2 C rate, respectively. The empty bullets (○) represent the discharge capacity and circle bullets (•) represent the Coulombic efficiency. Cells in e. were activated at 0.05 C rate while cells in f. were activated at 0.1 C rate. g & h. self-discharge tests. The cells were cycled at 0.2 C for 9 cycles, stopped at 2.1 V during 10th discharge and rested for 3 days before the discharging process was resumed. Voltage-capacity profiles of the cells were


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recorded, suggesting the cell with CNTs/V2O5 RSL exhibit a dramatically reduced self-discharge rate. In addition, Figures 3e and 3f compares the electrochemical performance of the Li-S cells with sulfur loading of 6 mg cm-2 at 0.1 C rate and 0.2 C rate, respectively. At 0.1 C rate, the cells with CNTs RSL and Celgard PP separator deliver similar capacity and cycling stability, while the cell with the CNTs/V2O5 RSL exhibits significantly higher initial capacity at 0.05 C rate (1309 mAh g-1 vs. ~1105 mAh g-1) and capacity retained after 50 cycles at 0.1 C rate (1037 mAh g-1 vs. ~613 mAh g-1). Although the use of CNTs RSL improves the performance of cells with low sulfur loading (e.g., < 2 mg cm-2), improvement over PP separators could not be observed for cells with high-sulfur loading (e.g., 6 mg cm-2), which may be due to their low adsorption capacity for polysulfides. The initial specific capacities and sulfur contents of the lithium-sulfur cells are further calculated based on the total weight of the cathodes, which includes the weights of the carbon/sulfur composite, conductive agent, binder and RSL. As shown in the Supplementary Table 2, consideration of the weight contribution from the CNTs/V2O5 RSL only slightly reduces the sulfur content from 70.4% to 66.6%. Given that incorporating the CNTs/V2O5 RSL significantly enhances the utilization of sulfur, the specific capacity of the cathode with CNTs/V2O5 RSL is still much higher than those with CNTs RSL or Celgard PP separator (814 mAh g-1 vs. ~700 mAh g-1). Moreover, the enhancement in electrochemical performance becomes more pronounced at 0.2 C rate. The cell with the CNTs/V2O5 RSL delivers a capacity of 1323 mAh g-1 and an area capacity of 7.94 mAh cm-2 after the 1st activation cycle, and maintains ~100% Coulombic efficiency for 100 cycles. On the contrary, the cell with the CNTs RSL exhibits a lower capacity of 890 mAh g-1 during the 2nd cycle and failed after 12 cycles due to the shuttling effect. Owing to the high charge transfer resistance, the cell with Celgard PP separator lost most of its capacity after 6 cycles. This observation further confirms


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that CNTs reduce the charge transfer resistance of the electrodes; while V2O5 does endow the RSL with better blocking capability for polysulfides, alleviate lithium corrosion and dramatically extend the cycling life (>100 cycles vs. 12 cycles) of the cells. To compare current work with literatures, Supplementary Table 3 summarizes the work published on carbon-coated separators, which are based on physisorption of polysulfides on CNTs, graphene, carbon black, carbon fibers and porous carbons, as well as their composites with non-reactive inorganic moieties such as Al2O3 and TiO2. In contrast, our work utilizes both physisorption and chemical reaction to block the polysulfides, providing much higher polysulfide scavenging capability. The best-performance Li-S cells reported, which contained a similar sulfur loading of 6.3 mg cm-2 and used single-wall CNTs-coated separators, could provide an initial energy density of 214 Wh kg-1 with a capacity fading rate of 0.423% per cycle.19 With 100 wt-% lithium excess and E/S ratio of 5, the cell with CNTs/V2O5 RSL delivers a much higher initial energy density of 365 Wh kg-1 with a lower capacity fading rate of 0.303% per cycle, while the ones with CNTs RSL exhibits an energy density of 311 Wh kg-1 with a capacity fading rate of 0.77% per cycle. The comparison clearly distinguishes our work from current state of the art. As shown in Supplementary Figure 6, the energy density of Li-S cells increases with higher sulfur loadings, lower ratio between the volume of electrolyte and the mass loading of sulfur (E/S, µL/mg), as well as higher specific capacities of active materials. With further optimization of the ratio of E/S (e.g., E/S=3) and addition of electroactive solvent into the electrolyte, the specific capacity of sulfur may achieve 1500 mAh g-1 and the energy density of the cell can possibly reach up to 560 Wh kg-1, which could bring Li-S batteries to practical applications. To quantify the capacity contribution from V2O5 moieties, cells with lithium as the anode and CNTs/V2O5 RSL as the cathodes were assembled and tested under similar condition. It was


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found that the capacity contribution from the CNTs/V2O5 RSL is less than 1% of the overall capacity of the Li-S cells (Supplementary Table 4). Therefore, it is reasonable to conclude that the enhanced performance for the cells with CNTs/V2O5 RSL is mainly attributed from the polysulfide-scavenging effect and the enhanced conductivity. To further examine the scavenging effect, RSL were equilibrated in Li2S6 solutions with various concentrations and used as the cathodes. The amount of polysulfides scavenged was then determined electrochemically. It was found that maximum amount of Li2S6 scavenged by the CNTs RSL and CNTs/V2O5 RSL are 0.110 mg and 0.486 mg, respectively (Supplementary Figure 7A). Furthermore, the polysulfides scavenged by the RSL could be released and recaptured reversibly upon cycling between 2.8 V to 1.7 V (Supplementary Figure 7B, C). Upon cycling for 10 cycles, the CNTs RSL exhibited significantly capacity decay whereas the CNTs/V2O5 RSL retains the initial capacity (the amount of polysulfide scavenged), clearly indicating the outstanding scavenging and regenerative capability of the CNTs/V2O5 RSL. Besides the improved capacity, cycling stability and rate performance, the use of CNTs/V2O5 RSL also dramatically reduced the self-discharge rate of Li-S cells. After cycling at 0.2 C rate for 9 cycles, the 10th discharge was stopped at 2.1 V, a voltage corresponding to maximized concentration of polysulfides in the cells.40,41 Then the discharging process was resumed after 3 days, during which the diffusion of polysulfides could cause self-discharge of the cells. Figures 3g and 3h display the charge-discharge voltage vs. capacity for cells without and with the CNTs/V2O5 RSL before and after the resting. As can be seen here, the cell without the RSL exhibits a discharge capacity of 674 mAh g-1 in the 9th cycle (denoted as C9th), which decreases to 539 mAh g-1 after the resting (denoted as C10th). On the contrary, the cell with the RSL delivers a much higher capacity of 1174 mAh g-1 in the 9th cycle (C9th), and still maintains


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the high capacity after the resting (1145 mAh g-1, C10th). For quantitative analysis, the selfdischarge rate of the cells can be estimated by (C9th-C10th)/C9th・100%. Upon incorporating the RSL, the self-discharge rate of the cell was decreased from 26.7% to 2.5%, suggesting the significant role of the CNTs/V2O5 RSL in blocking diffusion of polysulfides and minimizing the self-discharge rate, which is essential for practical utilization of lithium-sulfur batteries.

SEM study of the scavenging and regeneration process. To further understand the scavenging and regenerating process, distribution of sulfur moieties within the CNTs/V2O5 RSL at different electrochemical stages was analyzed with SEM and energy dispersive x-ray (EDX) spectroscopy. Li-S cells with CNTs/V2O5 RSL were cycled at 0.3 C and interrupted at 2.05 V during discharging or 2.60 V during charging, respectively. The CNTs/V2O5 RSL were then disassembled from the cells and dried in an argon-filled glove box for SEM and EDX studies.

Figure 4. SEM image and element-mapping of CNTs/V2O5 RSL at discharged and charged stages. Li-S cells were cycled at 0.3 C between 1.7 to 2.8 V and a. interrupted at 2.05 V during the discharging or b. interrupted at 2.60 V during the charging. The blue arrows show the direction of the line scan, while the blue circles represent the starting and ending points. Purple line represents sulfur and orange line represents vanadium. Scale bars are a. 20 µm and b. 25 µm.


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Figure 4a displays a cross-section SEM image and the corresponding EDX analysis of the RSL interrupted at 2.05 V. At this electrochemical stage, sulfur is mainly converted to polysulfides located within the electrode and in the electrolyte. EDX analysis shows two peaks associated with sulfur and vanadium co-localized in the center, indicating that the sulfur moieties are distributed dominantly within the V2O5 layer (less amount of sulfur in the CNTs region). This observation is consistent with the critical role of V2O5 in scavenging the polysulfides. Figure 4b presents a cross-section SEM image and the corresponding EDX analysis of the RSL interrupted at 2.60 V. At this electrochemical stage, the scavenged polysulfides are partially stripped away while the RSL is being regenerated. Consistently, EDX analysis also shows two co-localized peaks for sulfur and vanadium but with significantly less amount of sulfur species. Consequently, the scavenging ability of CNTs/V2O5 RSL also alleviate the corrosion of lithium anodes during cycling. As shown in Supplementary Figures 8 and 9, the lithium anode from the cell with CNTs RSL exhibits a rough surface with a thick sulfur-containing passivation film (~300 µm). In comparison, the lithium anode from the cell with CNTs/V2O5 RSL maintains a smooth surface with a significantly thinner penetration of polysulfides (~80 µm depth), indicating 73.3% less lithium corrosion.

Reactions between V2O5 and polysulfides probed by XPS. The scavenging effect is supposed to originate from the chemical-physical adsorption and/or reactions between polysulfides and the CNTs/V2O5 RSL. To explore the mechanism, we used Li2S6 as a representative polysulfide species, which was mixed with V2O5 nanowires. The resulted oxide/sulfide solid was isolated and investigated using x-ray photoelectron spectroscopy (XPS) analysis. XPS spectra of V2O5 before and after mixing with Li2S6 are presented in Figures 5a and 5b,


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respectively. V2O5 displays a typical 2p3/2 spectrum for the V5+ state at 517.5 eV. After the mixing, the 2p3/2 peak splits into two peaks centered at 517.5 eV and 516.0 eV, which are originated from the V5+ and V4+ states, respectively.42 Figures 5c and 5d further compare the sulfur 2p core spectra of Li2S6 and oxide/sulfur solid. Li2S6 exhibits two sulfur states at 163.0 eV and 161.7 eV, which can be assigned to bridging (SB0) and terminal (ST-1) sulfur atoms in polysulfide anions, respectively.6,43,44 The ratio between SB0 and ST-1 is around 2:1, which is in accordance with the composition of Li2S6. In contrast, the S 2p spectrum of the oxide/sulfide solid illustrates two sulfur states, which can be attributed to SB0 at 163.2 eV and polythionate complex at 167.9 eV, respectively.43 The formation of V4+ and the polythionate complex suggests the occurrence of redox reactions between Li2S6 and V2O5, forming Li-V-O-S complexes. Meanwhile, the terminal sulfur atoms (ST-1) were not detected in the oxide/sulfide solid, suggesting that the Li+ ions, which were paired with the polysulfides, are intercalated or inserted into V2O5.

Figure 5. Reactions between V2O5 and polysulfides probed by XPS. a. Vanadium 2p3/2 spectra of V2O5 and b. V2O5/sulfide compound formed by reacting V2O5 with Li2S6, indicating the formation of V4+ in the presence of Li2S6. c. Sulfur 2p core spectra of Li2S6 showing the terminal (ST-1) and bridging (SB0) sulfur atoms with an expected ratio of 1:2. d. Sulfur 2p core spectra of the V2O5/sulfide compound. The formation of polythionate groups indicates redox reactions between Li2S6 and V2O5. 15 ACS Paragon Plus Environment

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Based on the studies presented above, a possible mechanism can be constructed: During discharging, soluble polysulfides are continuously generated in the cathode and tend to diffuse toward the anode. With the incorporation of CNTs/V2O5 RSL, polysulfides are adsorbed and oxidized by the embedded oxide, forming solid-state [Polysulfides-RSL] complex and being immobilized. In the subsequent charging/delithiation process, lithium ions and polysulfides are stripped away from the RSL and re-deposited onto the electrodes, respectively. Through such a dynamic and regenerative process, the shuttling effect of polysulfides can be effectively mitigated, leading to Li-S batteries with significantly improved electrochemical performance. Thermodynamically, adsorption occurs spontaneously between solid-gas and solid-liquid interfaces to balance the chemical potentials between the interfaces. In this regard, a series of metal oxides with distinct electronic structures were mixed with Li2S6 solutions and then centrifuged (see their digital photographs in Figure 6a). The Li2S6 solution (control) exhibits a dark brown color, while the mixtures containing CNTs, CeO2, ZnO, MgO, Al2O3, MoO3, TiO2, WO3, or V2O5 show increasingly lighter color, indicating an increasing degree of adsorption or reaction of the sulfides with oxides. This observation suggests that various oxides could be used as the blocking moieties for RSL fabrication. To understand the adsorption and chemical reaction of polysulfides with the RSL, Figure 6b compares the redox potentials of polysulfides (Eredox) with the conduction bands (Ec) of commonly used metal oxides.45–48 For Li-S batteries, the redox potentials of polysulfides exist in the range from 2.2 to 2.5 V (vs. Li+/Li) depending on their compositions,40 which is marked in Figure 6b. When the redox potential of the polysulfides is above the conduction bands of the oxide, electrons from the polysulfides can be transferred to the oxides, resulting in chemisorption with chemical-bond formations (Supplementary Figure 10). Based on the relative position of the


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conduction bands, such oxides can be categorized into two groups: one group that can physically adsorb polysulfides without electron transfer (physisorption) including MgO, Al2O3, SiO2, Li2O, CeO2, PbO, NiO and ZnO; the other group that can react with polysulfides (chemisorption) including SnO2, CoO, TiO2, Fe2O3, CuO, MnO2, MoO3, V2O5, WO3, and CrO3. For physisorption, the adsorption is mainly governed by work function (or surface energy, which is proportional to surface potential) of the oxides. An oxide with higher surface potential my build up a stronger electric field within its Debye length, resulting in a stronger adsorption of the adsorbates (Supplementary Figure 11).49 Figure 6c displays the work functions of a series of oxides,47 which can be used as an indicator for adsorption ability or polysulfide-scavenging capability. Comparing with MgO, CeO2 and ZnO, Al2O3 has the highest work function and the best polysulfide-scavenging performance as observed in the visual experiment, in which the Li2S6 solutions with MgO, CeO2 or ZnO remain brownish while that with Al2O3 shows light yellow color. In terms of the oxides with Ec lower than Eredox, chemisorption occurs, where the color of the Li2S6 solutions diminished immediately upon contacting with the oxides (MoO3, TiO2, WO3 and V2O5). Generally, the bond energy between adsorbents and adsorbates is related to their dissociation energy,50 electronegativity and chemical hardness,47 which can be calculated with Flore’s equation.51 It is reasonable to hypothesize that stronger bond energy between an oxide and the polysulfides should lead to better scavenging or blocking effect. To examine such hypothesis, a series of CNTs/oxide RSL were fabricated using CNTs and different oxides (see XRD in Supplementary Figure 12), and their polysulfide-scavenging capability was evaluated. Figure 6d presents their bond energies with polysulfides, as well as capacities of Li-S cells with such RSL after 100 cycles at 1C. As shown here, there is a significant correlation between bond


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energy and cycling stability: stronger bond energies between the oxides and polysulfides lead to higher capacity retentions and lower self-discharge rate (Supplementary Figure 13). For example, WO3 and polysulfides exhibit high bond energy of 13.62 eV, leading to cells with a high capacity of 1075 mAh g-1 and a near-zero self-discharge rate. CuO and polysulfides show lower bond energy of 9.83 eV, as expected, resulting in lower capacity retention of 572.9 mAh g1

and ~ 9.0% of self-discharge rate. This observation suggests that it is possible to use the bond

energy between the scavenging materials and polysulfides to evaluate or predict their polysulfide-scavenging capability, providing a quantified guidance for Li-S batteries.


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Figure 6. Correlations between cell performance, work function of oxide moieties and bond energy between the oxides and polysulfides. a. Photographs of Li2S6 solutions mixed with metal oxides after centrifugation. b. Absolute potentials of the conduction bands and valence bands of various metal oxides, as well as the oxidation potential of polysulfides (2.2 to 2.5 V vs. Li+/Li, labeled in purple). c. Work functions of a series metal oxides. d. A comparison of the bond energies between the metal oxides and polysulfides (Light green) with the specific capacity of the corresponding Li-S cells after 100 cycles at 1 C (Green). These cells were made using RSL containing these metal oxides, respectively. The bond energies were calculated with Flore’s equation based on dissociation energy, electronegativity and chemical hardness of metal oxides and polysulfides.


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Conclusion In summary, we have developed a class of RSL based on CNTs and oxides with lowdimension forms, which can dynamically block the diffusion of polysulfides and regenerate themselves during cycling. Li-S batteries with CNTs/V2O5 RSL exhibit high areal capacity of >6 mAh cm-2 for 60 cycles, dramatically extended cycling life (>100 cycles vs. 12 cycles), low selfdischarge rate of 2.45% after resting for 3 days and ~73.3% less lithium corrosion. With further optimization, energy density of the cell with RSL can possibly reach up to 560 Wh kg-1, which could bring Li-S batteries to practical applications. Rooting from the electronic structure of the oxides and the redox potentials of polysulfides, the scavenging capability of the oxides is thoroughly investigated and correlated with the electrochemical performance of Li-S cells. This work not only offers a class of polysulfide-scavenging layers to effectively address the shuttling effect, but also provides quantified design framework towards Li-S batteries with high energy density and prolonged cycling life, which brings them one step closer to practical applications.

Experimental methods Synthesis of CNTs/oxide composites: CNTs/V2O5 composites were synthesized with activated CNTs according to the previously reported procedure.37 Briefly, 0.6 g of ammonium metavanadate (Sigma-Aldrich) and 1 g of P123 (EO20PO70EO20) (Sigma-Aldrich) were dispersed in 60 mL deionized water with 3 mL 2 M HCl. 20 mg activated CNTs was added to the mixture and sonicated for 30 min. The mixture was stirred at room temperature for 12 h and then transferred to an autoclave and heated at 120 ˚C for 24 h. The resulted composites were rinsed with DI water and ethanol for 3 times, and dried at 80 ˚C overnight in vacuum. Other CNTs composites containing different metal oxides were synthesized using similar hydrothermal


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methods (see Supplementary Information for details). Fabrication of RSL: The RSL were prepared using a vacuum-filtration method. CNTs and CNTs/metal oxides composites were dispersed in ethanol by sonication and formed 0.1 mg mL-1 and 1 mg mL-1 suspensions, separately. Subsequently, 20 mL CNT suspension, 6 mL suspension of CNTs/metal oxides composites and 20 mL CNT suspension were vacuum filtered through a polypropylene membrane (Celgard 2500, diameter: 47 mm) and form a flexible triple layer membrane. The membranes were dried at 70 ˚C overnight and then punched into a round shape with diameter of 18 mm. The weight of the RSL on each separator is around 0.4-0.6 mg cm-2 (Supplementary Table 1). For CNTs RSL, 100 mL CNT suspension was filtrated. Preparation of sulfur cathodes and Li2S6 solution: Sulfur cathodes were prepared using a slurry casting method. For electrodes with low sulfur loading (1~2 mg cm-2), sulfur, carbon black and polyvinylidene fluoride (PVDF) were mixed with weight ratio of 5:4:1 to form a homogenous slurry with N-methyl-2-pyrrolidone, then casted onto carbon-coated aluminum foil with a doctor blade. For electrodes with higher sulfur loading (up to 6 mg cm-2), carbon/sulfur composites, carbon nanofiber, carbon black and PVDF were mixed with weight ratio of 88:4:1:7 to form a slurry. Porous carbon particles were fabricated using Kejent black52 and the carbon/sulfur composites were prepared using liquid infiltration method at 159 ˚C with a weight ratio of 1:4. The electrodes were dried at 70 ˚C in vacuum for 4 h and then cut into pieces with a diameter of 16 mm. 0.5 M Li2S6 solution was prepared by mixing stoichiometric amounts of elemental sulfur (Sigma Aldrich) and Li2S (Alfa Aesar) in DOL:DME (volume ratio 1:1). A homogenous darkred solution of Li2S6 was obtained after stirring for 24 h at 130 ˚C. Electrochemical measurements: To evaluate the electrochemical performance, 2032-type coin cells (MTI Corporation) were assembled using lithium metal as the anodes. RSL were placed


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between polypropylene separator and sulfur cathode. 0.5 M LiTFSI and 2 wt-% LiNO3 in DOL/DME was used as electrolyte. CV measurements were performed on a Bio-Logic VMP3 electrochemical workstation. Galvanostatic charge-discharge measurements were carried out using Land CT2000 battery tester in a voltage range of 1.7-2.8 V for all rates. Specific capacities were calculated with respect to the mass of sulfur. EIS tests were carried out on a Solartron 1860/1287 Electrochemical Interface. Material characterizations: XRD measurements were performed on Rigaku MiniFlex instrument using the copper Kα radiation (λ = 1.54 Å). TGA was performed on a TA Instrument SDT Q600 employing a heating rate of 5 ˚C min-1 from 40 ˚C to 600 ˚C under airflow. SEM studies were conducted on a JEOL JSM-6700 FE-SEM and TEM studies were carried out on a FEI T12 operating at 120 kV. For XPS studies, the samples were sealed in a transporter in the glove box before being quickly transferred to the high-vacuum chamber of XPS (AXIS Ultra DLD) for analysis. All the spectra were fitted to Gaussian-Lorentzian functions and a Shirley-type background using CasaXPS software. The binding energy values were all calibrated using C 1s peak at 285.0 eV.


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ASSOCIATED CONTENT Supporting Information. The supporting information is available free of charge on the ACS Publications website. Synthesis and characterizations of CNTs composites with different metal oxides; Composition and thickness of each RSL; Galvanostatic cycling performances and self-discharge rates of lithium-sulfur batteries with different RSL; Calculation of energy densities for lithiumsulfur batteries; SEM images of lithium anodes after cycling; Electron transfer directions and interactions in physisorption and chemisorption (PDF).

AUTHOR INFORMATION Corresponding author Email: [email protected] Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work is supported by the Center of HK Graphene Technology and Energy Storage. We would thank Zheng Chen and Xiaolei Wang for valuable discussions. We would also thank Yang Liu and Duo Xu for technical assistance.


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